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Nuclear magnetization, spin quantum number, NMR

sensitive isotopes, NMR signal generation, chemical


shifts, coupling effects, structural determination.
Introduction
Nuclear magnetic resonance is a phenomenon that
occurs when the nuclei of certain atoms are immersed
in a static magnetic field and exposed to a second
oscillating magnetic field.
Principles of NMR
Nuclei are composed of Neutrons and Protons.

When the spins of the protons and neutrons


comprising these nuclei are not paired, the overall spin
of the charged nucleus generates a magnetic dipole
along the spin axis.

The intrinsic magnitude of this dipole is a


fundamental nuclear property called the nuclear
magnetic moment, .
Principles of NMR
Nuclei are positively charged and spin on an axis; they
create a tiny magnetic field.

Normally the nuclear magnetic fields are randomly


oriented.

When placed in an external magnetic field (Bo), the


nuclear magnetic field can either be aligned with the
external magnetic or oppose the external magnetic
field.
Principles of NMR
Some nuclei experience this phenomenon, and others
do not, depending upon whether they possess a
property called spin, I.

I = 0 is NMR inactive.
Principles of NMR
The nuclear magnetic moment of a nucleus can align
with an externally applied magnetic field of strength
Bo in only 2I+1 ways, either re-inforcing or opposing
Bo.

The energy difference between aligned and opposed to


the external magnetic field (Bo) is generally small and
is dependant upon Bo.
Principles of NMR
The energetically preferred orientation has the
magnetic moment aligned parallel with the applied
field (spin +1/2) and is often given the notation a or
sometime called alpha.

The higher energy anti-parallel orientation (spin -


1/2) is referred to as b or beta.
Principles of NMR
Principles of NMR
Two nuclear spin states separated by E.
Lower energy statenuclear spin magnetic moment
aligned with Bo.
Higher energy statenuclear spin magnetic moment
aligned against Bo.

Application of RF radiation pulse causes spin to flip from


lower to higher energy state.
Principles of NMR
The nuclear magnetic resonance (NMR)
spectroscopy experiment involves using energy in
the form of radio waves to pump the excess alpha
oriented nuclei into the beta state.

When the energy is removed, the energized nuclei


relax back to the alpha state.

The fluctuation of the magnetic field associated


with this relaxation process is called resonance and
this resonance can be detected and converted into
the peaks we see in an NMR spectrum.
Principles of NMR
The frequency needed for resonance and the applied magnetic
field strength are proportionally related:

NMR spectrometers are referred to as 300 MHz instruments,


500 MHz instruments, and so forth, depending on the
frequency of the RF radiation used for resonance.
Principles of NMR
NMR spectrum
A NMR spectrum is a plot of the absorption(signal) at a
specific frequency (magnetic field strength).

The different positions of NMR absorptions are described as


chemical shifts ().

Different nuclear magnetic resonance spectrometers have


different magnetic field strengths.

Since different NMRs have different operating frequencies,


spectra cannot be compared from different machines if they
are reported in frequency units.
Example of NMR spectrum

Nuclei Nuclei
surrounded surrounded
by less by more
electron electron
density density
Chemical Shift
A chemical shift is defined as the difference in parts per
million (ppm).

It is calculated as the shift downfield from TMS in Hz, divided


by the spectrometer operating frequency in MHz.

Tetramethylsilane (TMS) is the most common reference


compound in NMR, it is set at = 0ppm.
Chemical shift

If a 60MHz spectrometer records a proton resonance


at a frequency of 426Hz downfield from TMS, this
corresponds to a chemical shift of 426/60 = 7.10ppm.
Interpreting a NMR spectrum
The number of peaks tells you the number of
different environments the hydrogen atoms are in.

The ratio of the areas under the peaks tells you the
ratio of the numbers of hydrogen atoms in each of
these environments.

The chemical shifts give you important information


about the sort of environment the hydrogen atoms are
in.

Multiplicity/Splitting pattern (n+1 rule)


Practice questions
1. For a nucleus with nuclear spin quantum number, I =1/2, what are the
values of mI?
A. +1/2, -1/2
B. +1/2,0
C. +1/2, +1
D. 0, +1

2. Which list below gives only spin active nuclei?


A. 2H, 12C, 19F
B. 1H, 13C, 19F
C. 1H, 2H, 12C
D. 1H, 12C, 19F

3. A nuclear magnetic resonance transition is shifted from the reference in a


400 MHz NMR spectrometer by 529 Hz. Calculate the chemical shift.
A. 5.29
B. 1.32
C. 7.56
D. 1.76
Practice questions
4. Electromagnetic radiation in the __________ region is used in 1H NMR
spectroscopy.
A. radio wave
B. ultraviolet
C. microwave
D. Infrared

5. The energy difference between the allowed spin states for an 1H nucleus is
__________ the strength of the external magnetic field in which it is placed.
A. exponentially related to
B. directly proportional to
C. inversely proportional to
D. logarithmically related to

6. __________ is commonly used as an internal reference in NMR


spectroscopy; its signal is assigned d = 0 in 1H and 13C NMR spectroscopy.

7. On a 90 MHz spectrometer, calculate the frequency at which a proton


absorbs if it appears at 4.20 ppm.
Practice questions (Answers)
1. A
2. B
3. B
4. A
5. B
6. TMS
7. 378